U.S. patent application number 17/290832 was filed with the patent office on 2021-12-16 for thermoplastic composition, electrical wire and article comprising the electrical wire.
The applicant listed for this patent is SHPP GLOBAL TECHNOLOGIES B.V.. Invention is credited to Mian DAI, Katsura HAYASHI, Tsutomu KINOSHITA, Kazuhiko MITSUI, Hariharan RAMALINGAM.
Application Number | 20210388202 17/290832 |
Document ID | / |
Family ID | 1000005854986 |
Filed Date | 2021-12-16 |
United States Patent
Application |
20210388202 |
Kind Code |
A1 |
DAI; Mian ; et al. |
December 16, 2021 |
THERMOPLASTIC COMPOSITION, ELECTRICAL WIRE AND ARTICLE COMPRISING
THE ELECTRICAL WIRE
Abstract
A thermoplastic composition includes an aromatic poly(ketone), a
poly(etherimide), and a reactive additive, wherein each component
is present in a particular amount as defined herein. The
thermoplastic composition can be useful in an insulating layer
disposed over a conductor wire to form an electrical wire. Articles
including the thermoplastic composition can be particularly useful
in applications including an electrical device component, a railway
vehicle component, an auto-mobile component, a marine vehicle
component, a construction component, construction component, a
building component, or an aircraft component.
Inventors: |
DAI; Mian; (Shanghai,
CN) ; MITSUI; Kazuhiko; (Tokyo, JP) ;
RAMALINGAM; Hariharan; (Bangalore, IN) ; KINOSHITA;
Tsutomu; (Tokyo, JP) ; HAYASHI; Katsura;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHPP GLOBAL TECHNOLOGIES B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
1000005854986 |
Appl. No.: |
17/290832 |
Filed: |
November 8, 2019 |
PCT Filed: |
November 8, 2019 |
PCT NO: |
PCT/IB2019/059625 |
371 Date: |
May 3, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62757442 |
Nov 8, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01B 1/02 20130101; H01B
3/427 20130101; C08L 2203/202 20130101; H01B 7/0275 20130101; C08L
2205/03 20130101; C08L 71/00 20130101 |
International
Class: |
C08L 71/00 20060101
C08L071/00; H01B 3/42 20060101 H01B003/42; H01B 7/02 20060101
H01B007/02 |
Claims
1. A thermoplastic composition comprising: 50 to 99.9 weight
percent of an aromatic poly(ketone); 0.1 to 50 weight percent of a
poly(etherimide); 0.1 to 20 weight percent of a reactive additive;
wherein weight percent of each component is based on the total
weight of the composition.
2. The thermoplastic composition of claim 1, wherein the aromatic
poly(ketone) comprises a poly(ether ketone), poly(ether ether
ketone), poly(ether ketone ketone), or a combination comprising at
least one of the foregoing.
3. The thermoplastic composition of claim 1, wherein the
poly(etherimide) comprises units of the formula ##STR00023##
wherein R is a substituted or unsubstituted C.sub.6-20 aromatic
hydrocarbon group, a substituted or unsubstituted straight or
branched chain C.sub.4-20 alkylene group, a substituted or
unsubstituted C.sub.3-8 cycloalkylene group, T is --O-- or a group
of the formula --O--Z--O-- wherein the divalent bonds of the --O--
or the --O--Z--O-- group are in the 3,3', 3,4', 4,3', or the 4,4'
positions, and Z is an aromatic C.sub.6-24 monocyclic or polycyclic
group optionally substituted with 1 to 6 C.sub.1-8 alkyl groups,
1-8 halogen atoms, or a combination comprising at least one of the
foregoing. ##STR00024##
4. The thermoplastic composition of claim 1, wherein the
polyetherimide is a copolymer further comprising units of the
formula ##STR00025## wherein each R' is independently a C.sub.1-13
monovalent hydrocarbyl group, each R.sup.4 is a C.sub.2-20
hydrocarbyl group, E of the siloxane is 2 to 50, the R and Z of the
imide are as in claim 3, and n is an integer from 5 to 100.
5. The thermoplastic composition of claim 1, wherein the reactive
additive is a polymeric additive comprising at least one reactive
end group.
6. The thermoplastic composition of claim 1, wherein the reactive
additive comprises a functionalized phenylene ether oligomer, an
epoxy resin, a novolac phenolic resin, or a combination
thereof.
7. The thermoplastic composition of claim 1, wherein the
composition further comprises up to 5 wt. % of an additive
composition.
8. The thermoplastic composition of claim 7, wherein the additive
composition comprises one or more of an antioxidant, a thermal
stabilizer, a hydrostabilizer, an ultraviolet absorber, a
processing aid, and a colorant.
9. The thermoplastic composition of claim 1, wherein the
composition exhibits one or more of: a crystallization temperature
greater than or equal to 250.degree. C., as measured from a molten
polymer mixture cooled at a rate of 20.degree. C./min; a melt
temperature of 250 to 450.degree. C.; a flexural modulus of greater
than 2500 MPa determined according to ASTM D 790; a flexural stress
of greater than 100 MPa, determined according to ASTM D 790; a
tensile stress of greater than 50 MPa determined according to ASTM
D 638; a HDT of greater than 100.degree. C., determined according
to ASTM D 648 at 1.82 MPa.
10. An electrical wire comprising: a conductor wire; and an
insulating layer disposed over the conductor wire, wherein the
insulating layer comprises an extrusion layer formed from the
thermoplastic composition of claim 1, optionally, wherein the
insulating layers further comprises one or more intervening layers
positioned between the conductor wire and the extrusion layer.
11. The electrical wire of claim 10, wherein the extrusion layer
coating the conductor wire has one or more of the following
properties: a tensile elongation of greater than 5%, a breakdown
voltage of greater than 10 kV; a adhesion strength of greater than
2.5 MPa.
12. The electrical wire of claim 10, wherein the conductor wire
comprises copper, aluminum, lead, gold, silver, iron, nickel,
chromium, or an alloy comprising at least one of the foregoing; and
the conductor wire has a rectangular cross-section.
13. The electrical wire of claim 10, wherein the extrusion layer
has a thickness of less than 250 micrometers.
14. An article comprising the electrical wire of claim 10.
15. The article of claim 14, wherein the article is an electrical
device component, a railway vehicle component, an auto-mobile
component, a marine vehicle component, a construction component,
construction component, a building component, or an aircraft
component.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Provisional
Application No. 62/757,442 filed on Nov. 8, 2018, incorporated by
reference herein in its entirety.
BACKGROUND
[0002] Aromatic poly(ketone)s such as poly(arylene ether ketone)s
are valued due to their resistance to high temperatures,
crystallizability, melt extrudability, and injection moldability,
thereby making them versatile and useful in many applications.
Properties such as strength, stiffness, chemical resistance, and
heat resistance can be tailored by blending other poly(ketone)s
with various other polymers in order to meet the requirements of a
wide variety of consumer products. However, many current aromatic
poly(ketone) compositions are less suitable for applications
requiring resistance to high heat, such as in certain consumer
electronics applications. Accordingly, there remains a continuing
need in the art for improved aromatic poly(ketone) compositions
having good mechanical properties, excellent heat and chemical
resistance, improved adhesion, and excellent electrical performance
for many industrial applications, especially in consumer
electronics.
SUMMARY
[0003] A thermoplastic composition comprises 50 to 99.9 weight
percent, or 60 to 95 weight percent, or 70 to 90 weight percent, or
70 to 80 weight percent of an aromatic poly(ketone); 0.1 to 50
weight percent, or 5 to 40 weight percent, or 10 to 30 weight
percent, or 15 to 25 weight percent of a poly(etherimide); 0.1 to
20 weight percent, or 0.5 to 10 weight percent, or 1 to 7 weight
percent, or 2 to 6 weight percent of a reactive additive; wherein
weight percent of each component is based on the total weight of
the composition.
[0004] An electrical wire comprises a conductor wire; and an
insulating layer disposed over the conductor wire, wherein the
insulating layer comprises an extrusion layer formed from the
thermoplastic composition, optionally, wherein the insulating
layers further comprises one or more intervening layers positioned
between the conductor wire and the extrusion layer.
[0005] An article comprises the electrical wire.
[0006] The above described and other features are exemplified by
the following detailed description.
DETAILED DESCRIPTION
[0007] The present disclosure is related to thermoplastic
compositions containing a combination of an aromatic poly(ketone),
a poly(etherimide), and a reactive additive. Unexpectedly, blends
of the aromatic poly(ketone), poly(etherimide), and reactive
additive can provide compositions with balanced mechanical
properties, heat and chemical resistance, and electrical
properties.
[0008] Accordingly, an aspect of the present disclosure is a
thermoplastic composition comprising 50 to 99.9 weight percent of
an aromatic poly(ketone), 0.1 to 50 weight percent of a
poly(etherimide), and 0.1 to 20 weight percent of a reactive
additive, wherein the amount of each component is based on the
total weight of the composition.
[0009] The aromatic poly(ketone) comprises repeating units of
formula (1)
##STR00001##
wherein Ar is independently at each occurrence a substituted or
unsubstituted, monocyclic or polycyclic aromatic group having 6-30
carbons. Exemplary Ar groups include, but are not limited to,
substituted or unsubstituted phenyl, tolyl, naphthyl, and biphenyl.
Unsubstituted phenyl is preferred. In some embodiments, the
aromatic poly(ketone) can be a poly(arylene ether ketone) (PAEK)
comprising repeating units of formula (1) and formula (2)
--Ar--O-- (2)
wherein Ar is defined as above. In some embodiments the aromatic
polyketone comprises a poly(ether ketone). A poly(ether ketone)
comprises repeating units of formula (3)
##STR00002##
wherein Ar is defined as above and Ar.sup.1 is independently at
each occurrence a substituted or unsubstituted, monocyclic or
polycyclic aromatic group having 6-30 carbons. Ar can be the same
as or different from Ar.sup.1. In some preferred embodiments Ar and
Ar.sup.1 are phenyl groups, preferably unsubstituted phenyl
groups.
[0010] In some embodiments, the aromatic poly(ketone) comprises a
poly(ether ether ketone). A poly(ether ether ketone) comprises
repeating units of formula (4)
##STR00003##
wherein Ar and Ar.sup.1 are defined as above. Ar.sup.2 is
independently at each occurrence a substituted or unsubstituted,
monocyclic or polycyclic aromatic group having 6-30 carbons. Ar,
Ar.sup.1, and Ar.sup.2 can be the same as or different from each
other. Additionally, two of Ar, Ar.sup.1, and Ar.sup.2 can be the
same as each other and the third can be different. In some
embodiments Ar, Ar.sup.1, and Ar.sup.2 are phenyl groups,
preferably unsubstituted phenyl groups.
[0011] Poly(arylene ether ketone)s are generally known, with many
examples being commercially available. Examples of commercially
available aromatic poly(ketone)s include those sold under the trade
name PEEK.TM., available from VICTREX.
[0012] In an aspect, the aromatic poly(ketone) comprises a
poly(ether ketone), poly(ether ether ketone), poly(ether ketone
ketone), or a combination comprising at least one of the foregoing,
preferably a poly(ether ether ketone) of formula (4).
[0013] The thermoplastic composition includes the aromatic
poly(ketone) in an amount of 50 to 99.9 weight percent. Within this
range, the aromatic poly(ketone) can be present in an amount of at
least 60 weight percent, or at least 70 weight percent. Also within
this range, the aromatic poly(ketone) can be present in an amount
of up to 95 weight percent, or up to 90 weight percent, or up to 80
weight percent.
[0014] In addition to the aromatic poly(ketone), the thermoplastic
composition further comprises a poly (etherimide).
Poly(etherimide)s comprise more than 1, for example 2 to 1000, or 5
to 500, or 10 to 100 structural units of formula (5)
##STR00004##
wherein each R is independently the same or different, and is a
substituted or unsubstituted divalent organic group, such as a
substituted or unsubstituted C.sub.6-20 aromatic hydrocarbon group,
a substituted or unsubstituted straight or branched chain
C.sub.4-20 alkylene group, a substituted or unsubstituted C.sub.3-8
cycloalkylene group, in particular a halogenated derivative of any
of the foregoing. In some embodiments R is divalent group of one or
more of the following formulas (6)
##STR00005##
wherein Q.sup.1 is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y is an integer from 1
to 5 or a halogenated derivative thereof (which includes
perfluoroalkylene groups), or --(C.sub.6H.sub.10).sub.z-- wherein z
is an integer from 1 to 4. In some embodiments R is m-phenylene,
p-phenylene, or a diarylene sulfone, in particular
bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone,
bis(3,3'-phenylene)sulfone, or a combination comprising at least
one of the foregoing. In some embodiments, at least 10 mole percent
or at least 50 mole percent of the R groups contain sulfone groups,
and in other embodiments no R groups contain sulfone groups.
[0015] Further in formula (5), T is --O-- or a group of the formula
--O--Z--O-- wherein the divalent bonds of the --O-- or the
--O--Z--O-- group are in the 3,3', 3,4', 4,3', or the 4,4'
positions, and Z is an aromatic C.sub.6-24 monocyclic or polycyclic
moiety optionally substituted with 1 to 6 C.sub.1-8 alkyl groups, 1
to 8 halogen atoms, or a combination comprising at least one of the
foregoing, provided that the valence of Z is not exceeded.
Exemplary groups Z include groups of formula (7)
##STR00006##
wherein R.sup.a and R.sup.b are each independently the same or
different, and are a halogen atom or a monovalent C.sub.1-6 alkyl
group, for example; p and q are each independently integers of 0 to
4; c is 0 to 4; and X.sup.a is a bridging group connecting the
hydroxy-substituted aromatic groups, where the bridging group and
the hydroxy substituent of each C.sub.6 arylene group are disposed
ortho, meta, or para (specifically para) to each other on the
C.sub.6 arylene group. The bridging group X.sup.a can be a single
bond, --O--, --S--, --S(O)--, --S(O).sub.2--, --C(O)--, or a
C.sub.1-18 organic bridging group. The C.sub.1-18 organic bridging
group can be cyclic or acyclic, aromatic or non-aromatic, and can
further comprise heteroatoms such as halogens, oxygen, nitrogen,
sulfur, silicon, or phosphorous. The C.sub.1-18 organic group can
be disposed such that the C.sub.6 arylene groups connected thereto
are each connected to a common alkylidene carbon or to different
carbons of the C.sub.1-18 organic bridging group. A specific
example of a group Z is a divalent group of formula (7a)
##STR00007##
wherein Q is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, or --C.sub.yH.sub.2y-- wherein y is an integer
from 1 to 5 or a halogenated derivative thereof (including a
perfluoroalkylene group). In a specific embodiment Z is a derived
from bisphenol A, such that Q in formula (7a) is
2,2-isopropylidene.
[0016] In an embodiment in formula (5), R is m-phenylene,
p-phenylene, or a combination comprising at least one of the
foregoing, and T is O--Z--O-- wherein Z is a divalent group of
formula (7a). Alternatively, R is m-phenylene, p-phenylene, or a
combination comprising at least one of the foregoing, and T is
O--Z--O wherein Z is a divalent group of formula (7a) and Q is
2,2-isopropylidene. Such materials are available under the trade
name ULTEM from SABIC. Alternatively, the polyetherimide can be a
copolymer comprising additional structural polyetherimide units of
formula (5) wherein at least 50 mole percent (mol %) of the R
groups are bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone,
bis(3,3'-phenylene)sulfone, or a combination comprising at least
one of the foregoing and the remaining R groups are p-phenylene,
m-phenylene or a combination comprising at least one of the
foregoing; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a
bisphenol A moiety, an example of which is commercially available
under the trade name EXTEM from SABIC.
[0017] In some embodiments, the poly(etherimide) is a copolymer
that optionally comprises additional structural imide units that
are not polyetherimide units, for example imide units of formula
(8)
##STR00008##
wherein R is as described in formula (5) and each V is the same or
different, and is a substituted or unsubstituted C.sub.6-20
aromatic hydrocarbon group, for example a tetravalent linker of the
formulas
##STR00009##
wherein W is a single bond, --O--, --S--, --C(O)--, --SO.sub.2--,
--SO--, a C.sub.1-18 hydrocarbylene group, --P(R.sup.a)(.dbd.O)--
wherein R.sup.a is a C.sub.1-8 alkyl or C.sub.6-12 aryl, or
--C.sub.yH.sub.2y-- wherein y is an integer from 1 to 5 or a
halogenated derivative thereof (which includes perfluoroalkylene
groups). These additional structural imide units preferably
comprise less than 20 mol % of the total number of units, and more
preferably can be present in amounts of 0 to 10 mol % of the total
number of units, or 0 to 5 mol % of the total number of units, or 0
to 2 mole % of the total number of units. In some embodiments, no
additional imide units are present in the poly(etherimide).
[0018] The poly(etherimide) can be prepared by any of the methods
known to those skilled in the art, including the reaction of an
aromatic bis(ether anhydride) of formula (9) or a chemical
equivalent thereof, with an organic diamine of formula (10)
##STR00010##
[0019] wherein T and R are defined as described above. Copolymers
of the polyetherimides can be manufactured using a combination of
an aromatic bis(ether anhydride) of formula (9) and an additional
bis(anhydride) that is not a bis(ether anhydride), for example
pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone
dianhydride.
[0020] Illustrative examples of aromatic bis(ether anhydride)s
include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride
(also known as bisphenol A dianhydride or BPADA),
3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone
dianhydride; 4,4'-(hexafluoroisopropylidene)diphthalic anhydride;
and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl
sulfone dianhydride. A combination of different aromatic bis(ether
anhydride)s can be used.
[0021] Examples of organic diamines include 1,4-butane diamine,
1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine,
1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine,
1,12-dodecanediamine, 1,18-octadecanediamine,
3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,
4-methylnonamethylenediamine, 5-methylnonamethylenediamine,
2,5-dimethylhexamethylenediamine,
2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine,
N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine,
1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide,
1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane,
m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene,
2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine,
2-methyl-4,6-diethyl-1,3-phenylene-diamine,
5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,
1,5-diaminonaphthalene, bis(4-aminophenyl) methane,
bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl)
propane, 2,4-bis(p-amino-t-butyl) toluene,
bis(p-amino-t-butylphenyl) ether, bis(p-methyl-o-aminophenyl)
benzene, bis(p-methyl-o-aminopentyl) benzene, 1,
3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide,
bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl
sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of
the foregoing compounds can be used. C.sub.1-4 alkylated or
poly(C.sub.1-4)alkylated derivatives of any of the foregoing can be
used, for example a polymethylated 1,6-hexanediamine. Combinations
of these compounds can also be used. In some embodiments the
organic diamine is m-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
3,3'-diaminodiphenyl sulfone, or a combination thereof.
[0022] The poly(etherimide) can include poly(siloxane-etherimide)
copolymers comprising polyetherimide units of formula (5) and
siloxane blocks of formula (11)
##STR00011##
wherein E has an average value of 2 to 100, 2 to 31, 5 to 75, 5 to
60, 5 to 15, or 15 to 40, each R' is independently a C.sub.1-13
monovalent hydrocarbyl group. For example, each R' can
independently be a C.sub.1-13 alkyl group, C.sub.1-13 alkoxy group,
C.sub.2-13 alkenyl group, C.sub.2-13 alkenyloxy group, C.sub.3-6
cycloalkyl group, C.sub.3-6 cycloalkoxy group, C.sub.6-14 aryl
group, C.sub.6-10 aryloxy group, C.sub.7-13 arylalkyl group,
C.sub.7-13 arylalkoxy group, C.sub.7-13 alkylaryl group, or
C.sub.7-13 alkylaryloxy group. The foregoing groups can be fully or
partially halogenated with fluorine, chlorine, bromine, or iodine,
or a combination comprising at least one of the foregoing. In an
embodiment no bromine or chlorine is present, and in another
embodiment no halogens are present. Combinations of the foregoing R
groups can be used in the same copolymer. In an embodiment, the
polysiloxane blocks comprises R' groups that have minimal
hydrocarbon content. In a specific embodiment, an R' group with a
minimal hydrocarbon content is a methyl group.
[0023] The poly (siloxane-etherimide)s can be formed by
polymerization of an aromatic bis(ether anhydride) of formula (9)
and a diamine component comprising an organic diamine (10) as
described above or a combination of diamines, and a polysiloxane
diamine of formula (12)
##STR00012##
wherein R' and E are as described in formula (11), and R.sup.4 is
each independently a C.sub.2-C.sub.20 hydrocarbon, in particular a
C.sub.2-C.sub.20 arylene, alkylene, or arylenealkylene group. In an
embodiment R.sup.4 is a C.sub.2-C.sub.20 alkylene group,
specifically a C.sub.2-C.sub.10 alkylene group such as propylene,
and E has an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15,
or 15 to 40. Procedures for making the polysiloxane diamines of
formula (12) are well known in the art.
[0024] In some poly(siloxane-etherimide)s the diamine component can
contain 10 to 90 mole percent (mol %), or 20 to 50 mol %, or 25 to
40 mol % of polysiloxane diamine (12) and 10 to 90 mol %, or 50 to
80 mol %, or 60 to 75 mol % of diamine (10), for example as
described in U.S. Pat. No. 4,404,350. The diamine components can be
physically mixed prior to reaction with the bisanhydride(s), thus
forming a substantially random copolymer. Alternatively, block or
alternating copolymers can be formed by selective reaction of (10)
and (12) with aromatic bis(ether anhydrides (9), to make polyimide
blocks that are subsequently reacted together. Thus, the
poly(siloxane-imide) copolymer can be a block, random, or graft
copolymer. In an embodiment the copolymer is a block copolymer.
[0025] Examples of specific poly(siloxane-etherimide)s are
described in U.S. Pat. Nos. 4,404,350, 4,808,686 and 4,690,997. In
an embodiment, the poly(siloxane-etherimide) has units of formula
(13)
##STR00013##
wherein R' and E of the siloxane are as in formula (11), R and Z of
the imide are as in formula (5), R.sup.4 is as in formula (12), and
n is an integer from 5 to 100. In a specific embodiment of the
poly(siloxane-etherimide), R of the etherimide is a phenylene, Z is
a residue of bisphenol A, R.sup.4 is n-propylene, E is 2 to 50, 5,
to 30, or 10 to 40, n is 5 to 100, and each R' of the siloxane is
methyl.
[0026] The relative amount of poly(siloxane) units and etherimide
units in the poly(siloxane-etherimide) depends on the desired
properties, and are selected using the guidelines provided herein.
In particular, as mentioned above, the block or graft
poly(siloxane-etherimide) copolymer is selected to have a certain
average value of E, and is selected and used in amount effective to
provide the desired wt % of poly(siloxane) units in the
composition. In an embodiment the poly(siloxane-etherimide)
comprises 10 to 50 wt %, 10 to 40 wt %, or 20 to 35 wt %
poly(siloxane) units, based on the total weight of the
poly(siloxane-etherimide).
[0027] The poly(etherimide)s can have a melt index of 0.1 to 10
grams per minute (g/min), as measured by American Society for
Testing Materials (ASTM) D1238 at 340 to 370.degree. C., using a
6.7 kilogram (kg) weight. In some embodiments, the poly(etherimide)
has a weight average molecular weight (Mw) of 1,000 to 150,000
grams/mole (Dalton), as measured by gel permeation chromatography,
using polystyrene standards. In some embodiments the
poly(etherimide) has an Mw of 10,000 to 80,000 Daltons. Such
poly(etherimide)s typically have an intrinsic viscosity greater
than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to
0.7 dl/g as measured in m-cresol at 25.degree. C.
[0028] The thermoplastic composition includes the poly(etherimide)
in an amount of 0.1 to 50 weight percent. Within this range, the
poly(etherimide) can be present in an amount of at least 5 weight
percent, or at least 10 weight percent, or at least 15 weight
percent. Also within this range, the poly(etherimide) can be
present in an amount of up to 40 weight percent, or up to 30 weight
percent, or up to 25 weight percent.
[0029] In addition to the aromatic poly(ketone) and the
poly(etherimide), the thermoplastic composition further comprises a
reactive additive. The reactive additive comprises one or more
reactive moieties including, but not limited to, a carboxyl group,
a hydroxyl group, an amine group, an anhydride group, a mercapto
group, a phenolic group, an ester group, an isocyanate group, an
epoxy group, a (meth)acrylic group, or a combination thereof. In an
aspect, the reactive additive can be a polymeric additive
comprising at least one reactive end group. Preferably, the
reactive end group on the polymeric additive comprises a carboxyl
group, a hydroxyl group, an amine group, an anhydride group, a
mercapto group, a phenolic group, an ester group, an isocyanate
group, an epoxy group, a (meth)acrylic group, or a combination
thereof, more preferably a phenolic group, an epoxy group, or a
(meth)acrylic group.
[0030] In a specific embodiment, the reactive additive can be a
functionalized phenylene ether oligomer, an epoxy resin, a novolac
phenolic resin, or a combination thereof. The phenylene ether
oligomer comprises phenylene ether repeating units of formula
(14)
##STR00014##
wherein for each repeating unit, each Z.sup.1 is independently
halogen, unsubstituted or substituted C.sub.1-12 hydrocarbyl
provided that the hydrocarbyl group is not tertiary hydrocarbyl,
C.sub.1-12 hydrocarbylthio, C.sub.1-12 hydrocarbyloxy, or
C.sub.2-12 halohydrocarbyloxy wherein at least two carbon atoms
separate the halogen and oxygen atoms; and each Z.sup.2 is
independently hydrogen, halogen, unsubstituted or substituted
C.sub.1-12 hydrocarbyl provided that the hydrocarbyl group is not
tertiary hydrocarbyl, C.sub.1-12 hydrocarbylthio, C.sub.1-12
hydrocarbyloxy, or C.sub.2-12 halohydrocarbyloxy wherein at least
two carbon atoms separate the halogen and oxygen atom. In some
embodiments, the poly(phenylene ether) oligomer comprises
2,6-dimethyl-1,4-phenylene ether repeating units.
[0031] The phenylene ether oligomer can be monofunctional or
bifunctional. For example, it can have at least a functional group
at one terminus of the polymer chain. The functional group can be
as described above, and preferably is a hydroxyl group or a
(meth)acrylate group. In some embodiments, the phenylene ether
oligomer comprises poly(2,6-dimethyl-1,4-phenylene ether). An
example of a monofunctional poly(2,6-dimethyl-1,4-phenylene ether)
oligomer is NORYL.TM. Resin SA120, available from SABIC.
[0032] In some embodiments, the phenylene ether oligomer can be
bifunctional. For example, it can have functional groups at both
termini of the oligomer chain. The functional groups can be, for
example, hydroxyl groups or (meth)acrylate groups. Bifunctional
polymers with functional groups at both termini of the polymer
chains are also referred to as "telechelic" polymers. In some
embodiments, the phenylene ether oligomer comprises a bifunctional
phenylene ether oligomer of formula (15)
##STR00015##
wherein Q.sup.1 and Q.sup.2 are each independently halogen,
unsubstituted or substituted C.sub.1-12 primary or secondary
hydrocarbyl, C.sub.1-12 hydrocarbylthio, C.sub.1-12 hydrocarbyloxy,
and C.sub.2-12 halohydrocarbyloxy wherein at least two carbon atoms
separate the halogen and oxygen atoms; each occurrence of Q.sup.3
and Q.sup.4 is independently hydrogen, halogen, unsubstituted or
substituted C.sub.1-12 primary or secondary hydrocarbyl, C.sub.1-12
hydrocarbylthio, C.sub.1-12 hydrocarbyloxy, and C.sub.2-12
halohydrocarbyloxy wherein at least two carbon atoms separate the
halogen and oxygen atoms; x and y are independently 0 to 30,
specifically 0 to 20, more specifically 0 to 15, still more
specifically 0 to 10, even more specifically 0 to 8, provided that
the sum of x and y is at least 2, specifically at least 3, more
specifically at least 4; L has the structure according to formula
(16)
##STR00016##
wherein each occurrence of R.sup.3 and R.sup.4 and R.sup.5 and
R.sup.6 is independently hydrogen, halogen, unsubstituted or
substituted C.sub.1-12 primary or secondary hydrocarbyl, C.sub.1-12
hydrocarbylthio, C.sub.1-12 hydrocarbyloxy, and C.sub.2-12
halohydrocarbyloxy wherein at least two carbon atoms separate the
halogen and oxygen atoms; z is 0 or 1; Y has a structure of
##STR00017##
wherein each occurrence of R.sup.a, R.sup.b, R.sup.c, R.sup.d, and
R.sup.e is independently hydrogen, C.sub.1-C.sub.12 hydrocarbyl, or
C.sub.1-C.sub.6 hydrocarbylene, optionally wherein R.sup.a and
R.sup.b or R.sup.c and R.sup.d together are a C.sub.4-C.sub.8
cycloalkylene group. Further in formula (15), X is independently at
each occurrence a hydrogen or a (meth)acrylate group).
[0033] In some embodiments the phenylene ether oligomer comprises a
bifunctional phenylene ether oligomer of formula (17)
##STR00018##
wherein each occurrence of Q.sup.5 and Q.sup.6 is independently
methyl, di-n-butylaminomethyl, or morpholinomethyl; and each
occurrence of a and b is independently 0 to 20, with the proviso
that the sum of a and b is at least 2, and X is independently at
each occurrence a hydrogen or a (meth)acrylate group). An exemplary
bifunctional phenylene ether oligomer includes NORYL.TM. Resin SA90
and NORYL.TM. Resin SA9000, each available from SABIC.
[0034] The phenylene ether oligomer can have a number average
molecular weight of 500 to 7,000 grams per mole, and a weight
average molecular weight of 500 to 15,000 grams per mole, as
determined by gel permeation chromatography using polystyrene
standards. In some embodiments, the number average molecular weight
can be 750 to 4,000 grams per mole, and the weight average
molecular weight can be 1,500 to 9,000 grams per mole, as
determined by gel permeation chromatography using polystyrene
standards.
[0035] The reactive additive can comprise an epoxy resin. Epoxy
resins useful as reactive additives can be produced by reaction of
phenols or polyphenols with epichlorohydrin to form polyglycidyl
ethers. Examples of useful phenols for production of epoxy resins
include substituted or unsubstituted bisphenol A, bisphenol F,
hydroquinone, resorcinol, tris-(4-hydroxyphenyl)methane, and
novolac resins derived from phenol or o-cresol. Epoxy resins can
also be produced by reaction of aromatic amines, such as
p-aminophenol or methylenedianiline, with epichlorohydrin to form
polyglycidyl amines. In a specific aspect, the reactive additive
comprises an epoxy resin formed from reaction of bisphenol A with
epichlorohydrin.
[0036] The reaction additive can also comprise a novolac phenolic
resin. The novolac phenolic resin can be made by reacting a phenol
with formaldehyde. The term "phenol" as used herein includes
substituted and unsubstituted phenyl, aryl, and fused aromatic
rings having a hydroxyl group. The molar ratio of formaldehyde to
phenol is less than 1. In a specific embodiment, the phenol is
bisphenol A, and the resulting bisphenol A novolac resin can be a
hydroxyl group equivalence of 100 to 150 g/eq, or 110 to 130
g/eq.
[0037] The thermoplastic composition includes the reactive additive
in an amount of 0.1 to 20 weight percent. Within this range, the
reactive additive can be present in an amount of at least 0.5
weight percent, or at least 1 weight percent, or at least 2 weight
percent. Also within this range, the reactive additive can be
present in an amount of up to 10 weight percent, or up to 7 weight
percent or up to 6 weight percent.
[0038] In addition to the aromatic poly(ketone), the
poly(etherimide), and the reactive additive, the thermoplastic
composition can optionally further include an additive composition.
The additive composition comprises one or more additives selected
to achieve a desired property, with the proviso that the
additive(s) are also selected so as to not significantly adversely
affect a desired property of the thermoplastic composition. The
additive composition or individual additives can be mixed at a
suitable time during the mixing of the components for forming the
composition. The additive composition can include an impact
modifier, flow modifier, filler (e.g., a particulate
polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal),
reinforcing agent (e.g., glass fibers), antioxidant, heat
stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV
absorbing additive, plasticizer, lubricant, release agent (such as
a mold release agent), antistatic agent, anti-fog agent,
antimicrobial agent, colorant (e.g, a dye or pigment), surface
effect additive, radiation stabilizer, flame retardant, anti-drip
agent (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer
(TSAN)), or a combination thereof. For example, a combination of an
antioxidant, a thermal stabilizer, a hydrostabilizer, an
ultraviolet absorber, a processing aid, and a colorant can be used.
The additives are used in the amounts generally known to be
effective. For example, the total amount of the additive
composition (other than any impact modifier, filler, or reinforcing
agent) can be up to 5 weight percent, or 0.001 to 5 weight percent,
or 0.01 to 5 weight percent, each based on the total weight of the
thermoplastic composition.
[0039] The thermoplastic composition can be prepared by melt mixing
or a combination of dry blending and melt mixing. Melt mixing can
be performed in single or twin screw type extruders or similar
mixing devices which can apply a shear and heat to the components.
Melt mixing can be performed at a temperatures greater than or
equal to the melting temperatures of the copolymers and less than
the degradation temperatures of either of the copolymers.
[0040] All of the ingredients can be added initially to the
processing system. In some embodiments, the ingredients can be
added sequentially and/or through the use of one or more master
batches. It can be advantageous to apply a vacuum to the melt
through one or more vent ports in the extruder to remove volatile
impurities in the composition. In some embodiments melt-mixing is
performed using an extruder and the composition exits the extruder
in a strand or multiple strands. The shape of the strand is
dependent upon the shape of the die used and has no particular
limitation. In some embodiments the composition is the product of
melt-mixing the polymers and, when present, any additives. An
exemplary preparation of the thermoplastic composition is further
described in the working examples below.
[0041] The thermoplastic composition can exhibit one or more
advantageous properties. For example, the thermoplastic composition
can have a crystallization temperature greater than or equal to
250.degree. C., as measured from a molten polymer mixture cooled at
a rate of 20.degree. C./min. The thermoplastic composition can have
a melt temperature of 250 to 450.degree. C., more preferably 300 to
400.degree. C. The thermoplastic composition can have a flexural
modulus of greater than 2500 MPa, preferably greater than 3000 MPa
determined according to ASTM D 790. The thermoplastic composition
can have a flexural stress of greater than 100 MPa, preferably
greater than 125 MPa, determined according to ASTM D 790. The
thermoplastic composition can have a tensile stress of greater than
50 MPa, preferably greater than 75 MPa determined according to ASTM
D 638. The thermoplastic composition can have a heat deflection
temperature of greater than 100.degree. C., preferably greater than
150.degree. C. determined according to ASTM D 648 at 1.82 MPa.
[0042] The thermoplastic composition described herein can be
particularly useful in electrical wire applications. Accordingly,
an electrical wire comprising the thermoplastic composition is
another aspect of the present disclosure. The electrical wire
comprises a conductor wire and an insulating layer disposed over
the conductor wire, wherein the insulating layer comprises an
extrusion layer formed from the thermoplastic composition.
[0043] The composition is applied to the conductor wire by a
suitable method such as extrusion coating to form a coated wire.
For example, a coating extruder equipped with a screw, crosshead,
breaker plate, distributor, nipple, and die can be used. The melted
thermoplastic composition forms a covering disposed over a
circumference of the conductor wire. Extrusion coating can employ a
single taper die, a double taper die, other appropriate die or
combination of dies to position the conductor centrally and avoid
die lip build-up.
[0044] In some embodiments it can be useful to dry the
thermoplastic composition before extrusion coating. Exemplary
drying conditions are 60 to 150.degree. C. for 2 to 20 hours.
[0045] In some embodiments, during extrusion coating, the
thermoplastic composition is melt filtered, prior to formation of
the coating, through one or more filters. In some embodiments the
thermoplastic composition will have substantially no particles
greater than 80 micrometers in size. In some embodiments any
particulates present will be less than or equal to 40 micrometers
in size. In some embodiments there will be substantially no
particulates greater than 20 micrometers in size. The presence and
size of particulates can be determined using a solution of 1 gram
of thermoplastic composition dissolved in 10 milliliters of a
solvent, such as chloroform, and analyzing it using microscopy or
light scattering techniques. Substantially no particulates is
defined as having less than or equal to 3 particulates, or, more
specifically, less than or equal to 2 particulates, or, even more
specifically, less than or equal to 1 particulate per one gram
sample. Low levels of particulates are beneficial for giving a
layer of insulation on a coated wire that will not have
electrically conductive defects as well as providing coatings with
improved mechanical properties.
[0046] The extruder temperature during extrusion coating is
generally less than the degradation temperature of the aromatic
poly(ketone) and poly(etherimide). Additionally the processing
temperature is adjusted to provide a sufficiently fluid molten
composition to afford a covering for the conductor, for example,
higher than the softening point of the thermoplastic composition,
or more specifically at least 20.degree. C. higher than the melting
point of the thermoplastic composition.
[0047] After extrusion coating, the conductive wire is usually
cooled using a water bath, water spray, air jets or a combination
comprising one or more of the foregoing cooling methods. Exemplary
water bath temperatures are 20 to 90.degree. C., or 80 to
90.degree. C.
[0048] In some embodiments, the composition is applied to the
conductor wire to form a covering disposed over and in physical
contact with the conductor wire. In some embodiments, the
insulating layer can comprise one or more intervening layers
positioned between the conductor wire and the extrusion layer.
[0049] Any methods of coating a conductor wire that are generally
known can be used. In some embodiments, the composition is applied
to a conductor wire having one or more intervening layers between
the conductor wire and the covering to form the insulating layer
disposed over the conductor wire. For instance, an optional
adhesion promoting layer can be disposed between the conductor wire
and extrusion layer. In another example the conductor wire can be
coated with a metal deactivator prior to applying the extrusion
layer. Alternatively, a metal deactivator can be mixed with the
thermoplastic composition. In another example an intervening layer
comprises a thermoplastic or thermoset composition that, in some
cases, is foamed.
[0050] The conductor can comprise a single strand or a plurality of
strands. In some cases, a plurality of strands can be bundled,
twisted, braided, or a combination of the foregoing to form a
conductor. Additionally, the conductor can have various shapes such
as round or oblong. Suitable materials for the conductor wires
include, but are not limited to, copper, aluminum, lead, gold,
silver, iron, nickel, chromium, and alloys comprising at least one
of the foregoing metals. In an exemplary embodiment, the conductor
wire is copper. The conductor wire can also be coated with, e.g.,
tin, gold or silver. In some embodiments the conductor wire
comprises optical fibers.
[0051] The cross-sectional area of the conductor and thickness of
the covering can vary and is typically determined by the desired
application for the coated wire. The coated wire can be used as
coated wire without limitation, including, for example, for harness
wire for automobiles, wire for household electrical appliances,
wire for electric power, wire for instruments, wire for information
communication, wire for electric cars, as well as ships, airplanes,
and the like. Specific applications that can benefit from coated
electrical wires comprising the thermoplastic composition are those
requiring high-heat, thin-walled wire coatings, for example for
high-heat train, automobile, aircraft, and data transmission
applications. In some specific embodiments, an article can comprise
the electrical wire having a covering comprising the thermoplastic
composition, wherein the article is a railway vehicle component, an
automobile component, or an aircraft component.
[0052] In some embodiments the extrusion layer can have a thickness
of less than 250 micrometers, preferably less than 160 micrometers.
The longest dimension of a cross-sectional area of the conductor
wire can be, for example, 0.1 to 5 millimeters. For example, when
the conductor wire has a circular cross-sectional area, the
conductor wire can have a diameter of 0.1 to 1 millimeters. For
example, when the conductor wire has a rectangular cross-sectional
area, the longest dimension of the rectangular cross-section can be
1 to 5 millimeters.
[0053] Multiple coated wires can be combined to form a cable. The
cable can comprise additional protective elements, structural
elements, or a combination thereof. An exemplary protective element
is a jacket which surrounds the group of coated wires. The jacket
and the covering on the coated wires, singly or in combination, can
comprise the thermoplastic composition described herein. A
structural element is a typically non-conductive portion which
provides additional stiffness, strength, shape retention capability
or the like.
[0054] The extrusion layer coating the conductor wire can exhibit
one or more desirable properties. For example, the extrusion layer
coating the conductor wire can have a tensile elongation of greater
than 5%, preferably greater than or equal to 50%. The extrusion
layer coating the conductor wire can have a breakdown voltage of
greater than 10 kV, preferably greater than 13 kV, more preferably
greater than 15 kV. The extrusion layer coating the conductor wire
can have a adhesion strength of greater than 2.5 MPa, preferably
greater than or equal to 2.7 MPa, more preferably greater than or
equal to 3 MPa, even more preferably greater than 8 MPa.
[0055] Articles comprising the electrical wire represent another
aspect of the present disclosure. For example, the electrical wires
including the thermoplastic composition can be particularly useful
for an electrical device component, a railway vehicle component, an
auto-mobile component, a marine vehicle component, a construction
component, construction component, a building component, or an
aircraft component.
[0056] Shaped, formed, or molded articles comprising the
thermoplastic compositions are also provided, according to
embodiments. A method of making an article comprises blending the
components of the thermoplastic composition described herein to
provide a thermoplastic composition, and forming an article from
the thermoplastic composition. The thermoplastic compositions can
be molded into useful shaped articles by a variety of means such as
injection molding, extrusion, compression molding, rotational
molding, blow molding, or thermoforming. Other articles including
the thermoplastic composition can include, for example, computer
and business machine housings such as housings for monitors,
handheld electronic device housings such as housings for cell
phones, electrical connectors, and components of lighting fixtures,
ornaments, home appliances, roofs, greenhouses, sun rooms, swimming
pool enclosures, thin walled articles such as housing for
electronic devices and the like. Additional examples of articles
that can be formed from the compositions include electrical parts,
such as relays, and enclosures, consumer electronics such as
enclosures and parts for laptops, desktops, docking stations,
personal digital assistants (PDAs), digital cameras, desktops, and
telecommunications parts such as parts for base station terminals.
Further examples of articles that can be formed from compositions
include light guides, light guide panels, lenses, covers, sheets,
films, and the like, e.g., LED lenses, LED covers, and so
forth.
[0057] This disclosure is further illustrated by the following
examples, which are non-limiting.
EXAMPLES
[0058] Materials used for the following examples are described in
Table 1.
TABLE-US-00001 TABLE 1 Com- ponent Description Supplier PEEK
Poly(etheretherketone) commercially available Victrex as PEEK 150G
PEI-1 Poly(etherimide) having repeating units derived SABIC from
bisphenol A dianhydride and para-phenylene diamine, obtained as
ULTEM CRS5001 PEI-2 Poly(etherimide) having repeating units derived
SABIC from bisphenol A dianhydride and 4,4'-
diaminodiphenylsulfone, having a glass transition temperature of
247.degree. C., obtained as EXTEM VH1003 PEI-Si A
poly(etherimide-siloxane) block copolymer SABIC having a siloxane
content of 20 weight percent, based on the total weight of the
block copolymer, available as SILTEM 1700 PPE-OH Copolymer of
2,6-dimethylphenol and 2,2-bis(3,5- SABIC
dimethyl-4-hydroxyphenol)propane comprising a phenolic end group
ortho-substituted with a di-n-butylaminomethylene group; obtained
as NORYL SA90 PPE-MA Copolymer of 2,6-dimethylphenol and
2,2-bis(3,5- SABIC dimethyl-4-hydroxyphenol)propane comprising a
methacrylic end group; obtained as NORYL SA9000 BPADGE Bisphenol A
type epoxy resin, formed from DIC reaction of epichlorohydrin with
bisphenol A, Corp. obtained as EPICLON AM-040-P BPANR Bisphenol A
novolac resin having a hydroxyl group DIC equivalence of 118 g/eq,
a resin softening point of Corp. 130.degree. C., and a bifunctional
bisphenol A content of 25 wt. %, obtained Phenolite KH-6021
[0059] The compositions of the following examples were prepared by
compounding on a twin screw extruded. Each component was blended
together and fed into the main feeder. Strands of the compositions
were cut into pellets and then dried prior to molding and testing.
Compounding conditions are summarized in Table 2.
TABLE-US-00002 TABLE 2 Parameters Unit Set Values Zone 1 Temp
.degree. C. 50 Zone 2 Temp .degree. C. 150 Zone 3 Temp .degree. C.
350 Zone 4 Temp .degree. C. 370 Zone 5 Temp .degree. C. 370 Zone 6
Temp .degree. C. 370 Zone 7 Temp .degree. C. 370 Zone 8 Temp
.degree. C. 370 Zone 9 Temp .degree. C. 370 Zone 10 Temp .degree.
C. 370 Zone 11 Temp .degree. C. 370 Die Temp .degree. C. 370 Screw
speed rpm 400 Throughput kg/hr 15-30
[0060] Samples were injection molded using a FANUC injection
molding machine and according to the injection molding profiled
summarized in Table 3.
TABLE-US-00003 TABLE 3 Parameters Unit Set Values Cnd: Pre-drying
time Hour 4 Cnd: Pre-drying temp .degree. C. 150 Hopper temp
.degree. C. 70 Zone 1 temp .degree. C. 350-360 Zone 2 temp .degree.
C. 360-370 Zone 3 temp .degree. C. 370-380 Nozzle temp .degree. C.
375-385 Mold temp .degree. C. 140-180
[0061] Molded samples were tested according to the following test
methods.
[0062] Heat deflection temperature (HDT) was measured according to
ASTM D648 and using a testing stress of 1.82 MPa and a sample
thickness of 6.4 millimeters.
[0063] Notched IZOD impact strength (NII) was measured according to
ASTM D256 and using a pendulum energy of 5 lbf/ft.
[0064] Tensile properties were measured according to ASTM D638 and
using a test speed of 5 millimeters per minute.
[0065] Flexural properties were measured according to ASTM D790
using a test speed on 1.27 millimeters per minute and a sample
thickness of 6.4 millimeters.
[0066] Thermal properties, including Tg, Tm, and Tc, were measured
by differential scanning calorimetry (DSC) according to ISO11357
using a heating/cooling rate of 20.degree. C./min.
[0067] Specific gravity ("Sg") was measured according to ASTM
D792.
[0068] Test wire samples were made by extruding the specified
composition on a conductor wire with an enamel layer and an
adhesive layer using an extrusion die similar to the shape of the
conductor wire. In the present examples, a copper conductor wire
having a rectangular cross section with chamfered edges at four
corners was used. The conductor wire was coated with three layers:
an enamel layer, an adhesive layer, and an extruded layer
comprising the coating composition. The thickness of the coating
comprising the composition was 150.+-.10 micrometers. The breakdown
voltage (BDV) of the coating layer was tested according to JIS
C3216-5. Additionally, two pieces of each of the test wire samples
were brought into close contact with each other with plane contact
at the flat planes by using an impregnation varnish, such as epoxy
resin or epoxy ester resin followed by curing. The adhesion
strength with the varnish was tested according to a modified
version of JIS K6850 using the above sample in place of the
standard lap shear design.
[0069] Table 4 shows the compositions and the measured properties.
Component amounts are given in weight percent, based on the total
weight of the composition.
TABLE-US-00004 TABLE 4 Unit CE1 CE2 E1 E2 E3 E4 E5 E6 PEEK % 80 80
76.2 76.2 78.1 76.2 76.2 76.2 PEI-1 % 20 19.0 19.0 19.5 19.0 19.0
PEI-2 % 20 PEI-Si % 19.0 PPE-OH % 4.8 2.4 4.8 PPE-MA % 4.8 BPADGE %
4.8 BPANR % 4.8 Tg .degree. C. 158 156 153 153 156 148 155 Tc
.degree. C. 298 301 292 299 300 300 298 299 Tm .degree. C. 341.6
343.2 340.4 343.8 343.8 344.1 340.6 343.9 Tensile Stress MPa 90 93
92 88.7 82.3 86.6 83.4 90.1 Flexural MPa 143 147 151 146.4 140.7
133.3 151.2 138.7 Stress Flexural MPa 3251 3358 3326 3343 3344 3202
3726 3303 Modulus NII J/m 20 23 23 16.7 19.0 20.4 16.7 20.8 HDT,
.degree. C. 162 172 152 164.4 167.4 159.1 155.3 169.7 1.82 MPa Sg
g/cm3 1.28 1.29 1.27 1.27 1.28 1.26 1.28 1.27 Adhesion MPa 1.9 2.3
3.3 8* 9.5* 2.7 3.7 2.7 BDV KV 15.2 15.7 19.4 13.1 15.7 13.9 Wire %
50 60 68 8 Brittle 5 Elongation *The fracture mode on adhesion
surface is base material fracture, which is different from other
examples.
[0070] As shown in Table 4, compositions according to the examples
E1-E5 including a functional additive exhibit tensile stress of
greater than 80 MPa, flexural stress of greater than 130 MPa, NII
of greater than 15 J/m, and HDT of greater than 150.degree. C. The
test wire examples E2-E3 show base material fracture mode on
adhesion surface. The maximum reading of adhesion strength between
the varnish and the extruded composition was limited by the
underlying materials.
[0071] This disclosure further encompasses the following aspects,
which are non-limiting.
[0072] Aspect 1: A thermoplastic composition comprising: 50 to 99.9
weight percent, or 60 to 95 weight percent, or 70 to 90 weight
percent, or 70 to 80 weight percent of an aromatic poly(ketone);
0.1 to 50 weight percent, or 5 to 40 weight percent, or 10 to 30
weight percent, or 15 to 25 weight percent of a poly(etherimide);
0.1 to 20 weight percent, or 0.5 to 10 weight percent, or 1 to 7
weight percent, or 2 to 6 weight percent of a reactive additive;
wherein weight percent of each component is based on the total
weight of the composition.
[0073] Aspect 2: The thermoplastic composition of aspect 1, wherein
the aromatic poly(ketone) comprises a poly(ether ketone),
poly(ether ether ketone), poly(ether ketone ketone), or a
combination comprising at least one of the foregoing, preferably a
poly(ether ether ketone).
[0074] Aspect 3: The thermoplastic composition of aspect 1 or 2,
wherein the poly(etherimide) comprises units of the formula
##STR00019##
wherein R is a substituted or unsubstituted C.sub.6-20 aromatic
hydrocarbon group, a substituted or unsubstituted straight or
branched chain C.sub.4-20 alkylene group, a substituted or
unsubstituted C.sub.3-8 cycloalkylene group, T is --O-- or a group
of the formula --O--Z--O-- wherein the divalent bonds of the --O--
or the --O--Z--O-- group are in the 3,3', 3,4', 4,3', or the 4,4'
positions, and Z is an aromatic C.sub.6-24 monocyclic or polycyclic
group optionally substituted with 1 to 6 C.sub.1-8 alkyl groups,
1-8 halogen atoms, or a combination comprising at least one of the
foregoing; preferably, wherein R is a divalent group of the
formula
##STR00020##
wherein Q.sup.1 is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y is an integer from 1
to 5 or a halogenated derivative thereof (which includes
perfluoroalkylene groups), or --(C.sub.6H.sub.10).sub.z-- wherein z
is an integer from 1 to 4; and Z is a group derived from a
dihydroxy compound of the formula
##STR00021##
wherein R.sup.a and R.sup.b are each independently a halogen atom
or a monovalent C.sub.1-6 alkyl group; p and q are each
independently integers of 0 to 4; c is 0 to 4; and X.sup.a is a
single bond, --O--, --S--, --S(O)--, --SO.sub.2--, --C(O)--, or a
C.sub.1-18 organic bridging group.
[0075] Aspect 4: The thermoplastic composition of any one or more
of aspects 1 to 3, wherein the polyetherimide is a copolymer
further comprising units of the formula
##STR00022##
wherein each R' is independently a C.sub.1-13 monovalent
hydrocarbyl group, each R.sup.4 is a C.sub.2-20 hydrocarbyl group,
E of the siloxane is 2 to 50, 5, to 30, or 10 to 40, the R and Z of
the imide are as in aspect 3, and n is an integer from 5 to
100.
[0076] Aspect 5: The thermoplastic composition of any one or more
of aspects 1 to 4, wherein the reactive additive is a polymeric
additive comprising at least one reactive end group, preferably
wherein the reactive end group comprises a carboxyl group, a
hydroxyl group, an amine group, an anhydride group, a mercapto
group, a phenolic group, an ester group, an isocyanate group, an
epoxy group, a (meth)acrylic group, or a combination thereof, more
preferably wherein the reactive end group comprises a phenolic
group, an epoxy group, or a (meth)acrylic group.
[0077] Aspect 6: The thermoplastic composition of any one or more
of aspects 1 to 5, wherein the reactive additive comprises a
functionalized phenylene ether oligomer, an epoxy resin, a novolac
phenolic resin, or a combination thereof.
[0078] Aspect 7: The thermoplastic composition of any one or more
of aspects 1 to 6, wherein the composition further comprises up to
5 wt. % of an additive composition.
[0079] Aspect 8: The thermoplastic composition of aspect 7, wherein
the additive composition comprises one or more of an antioxidant, a
thermal stabilizer, a hydrostabilizer, an ultraviolet absorber, a
processing aid, and a colorant.
[0080] Aspect 9: The thermoplastic composition of any one or more
of aspects 1 to 8, wherein the composition exhibits one or more of:
a crystallization temperature greater than or equal to 250.degree.
C., as measured from a molten polymer mixture cooled at a rate of
20.degree. C./min; a melt temperature of 250 to 450.degree. C.,
more preferably 300 to 400.degree. C.; a flexural modulus of
greater than 2500 MPa, preferably greater than 3000 MPa determined
according to ASTM D 790; a flexural stress of greater than 100 MPa,
preferably greater than 125 MPa, determined according to ASTM D
790; a tensile stress of greater than 50 MPa, preferably greater
than 75 MPa determined according to ASTM D 638; a HDT of greater
than 100.degree. C., preferably greater than 150.degree. C.
determined according to ASTM D 648 at 1.82 MPa.
[0081] Aspect 10: An electrical wire comprising: a conductor wire;
and an insulating layer disposed over the conductor wire, wherein
the insulating layer comprises an extrusion layer formed from the
thermoplastic composition of any one or more of aspects 1 to 9,
optionally, wherein the insulating layers further comprises one or
more intervening layers positioned between the conductor wire and
the extrusion layer.
[0082] Aspect 11: The electrical wire of aspect 10, wherein the
extrusion layer coating the conductor wire has one or more of the
following properties: a tensile elongation of greater than 5%,
preferably greater than or equal to 50%; a breakdown voltage of
greater than 10 kV, preferably greater than 13 kV, more preferably
greater than 15 kV; a adhesion strength of greater than 2.5 MPa,
preferably greater than or equal to 2.7 MPa, more preferably
greater than or equal to 3 MPa, even more preferably greater than 8
MPa.
[0083] Aspect 12: The electrical wire of aspect 10 or 11, wherein
the conductor wire comprises copper, aluminum, lead, gold, silver,
iron, nickel, chromium, or an alloy comprising at least one of the
foregoing; and the conductor wire has a rectangular
cross-section.
[0084] Aspect 13: The electrical wire of any one or more of aspects
10 to 12, wherein the extrusion layer has a thickness of less than
250 micrometers, preferably less than 160 micrometers.
[0085] Aspect 14: An article comprising the electrical wire of any
one or more of aspects 10 to 13.
[0086] Aspect 15: The article of aspect 14, wherein the article is
an electrical device component, a railway vehicle component, an
auto-mobile component, a marine vehicle component, a construction
component, construction component, a building component, or an
aircraft component.
[0087] The compositions, methods, and articles can alternatively
comprise, consist of, or consist essentially of, any appropriate
materials, steps, or components herein disclosed. The compositions,
methods, and articles can additionally, or alternatively, be
formulated so as to be devoid, or substantially free, of any
materials (or species), steps, or components, that are otherwise
not necessary to the achievement of the function or objectives of
the compositions, methods, and articles.
[0088] All ranges disclosed herein are inclusive of the endpoints,
and the endpoints are independently combinable with each other.
"Combinations" is inclusive of blends, mixtures, alloys, reaction
products, and the like. The terms "first," "second," and the like,
do not denote any order, quantity, or importance, but rather are
used to distinguish one element from another. The terms "a" and
"an" and "the" do not denote a limitation of quantity, and are to
be construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. "Or"
means "and/or" unless clearly stated otherwise. Reference
throughout the specification to "some embodiments", "an
embodiment", and so forth, means that a particular element
described in connection with the embodiment is included in at least
one embodiment described herein, and may or may not be present in
other embodiments. The term "combination thereof" as used herein
includes one or more of the listed elements, and is open, allowing
the presence of one or more like elements not named. In addition,
it is to be understood that the described elements may be combined
in any suitable manner in the various embodiments.
[0089] Unless specified to the contrary herein, all test standards
are the most recent standard in effect as of the filing date of
this application, or, if priority is claimed, the filing date of
the earliest priority application in which the test standard
appears.
[0090] Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this application belongs. All cited
patents, patent applications, and other references are incorporated
herein by reference in their entirety. However, if a term in the
present application contradicts or conflicts with a term in the
incorporated reference, the term from the present application takes
precedence over the conflicting term from the incorporated
reference.
[0091] Compounds are described using standard nomenclature. For
example, any position not substituted by any indicated group is
understood to have its valency filled by a bond as indicated, or a
hydrogen atom. A dash ("-") that is not between two letters or
symbols is used to indicate a point of attachment for a
substituent. For example, --CHO is attached through carbon of the
carbonyl group.
[0092] As used herein, the term "hydrocarbyl", whether used by
itself, or as a prefix, suffix, or fragment of another term, refers
to a residue that contains only carbon and hydrogen. The residue
can be aliphatic or aromatic, straight-chain, cyclic, bicyclic,
branched, saturated, or unsaturated. It can also contain
combinations of aliphatic, aromatic, straight chain, cyclic,
bicyclic, branched, saturated, and unsaturated hydrocarbon
moieties. However, when the hydrocarbyl residue is described as
substituted, it may, optionally, contain heteroatoms over and above
the carbon and hydrogen members of the substituent residue. Thus,
when specifically described as substituted, the hydrocarbyl residue
can also contain one or more carbonyl groups, amino groups,
hydroxyl groups, or the like, or it can contain heteroatoms within
the backbone of the hydrocarbyl residue. The term "alkyl" means a
branched or straight chain, unsaturated aliphatic hydrocarbon
group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl,
t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" means a
straight or branched chain, monovalent hydrocarbon group having at
least one carbon-carbon double bond (e.g., ethenyl
(--HC.dbd.CH.sub.2)). "Alkoxy" means an alkyl group that is linked
via an oxygen (i.e., alkyl-O--), for example methoxy, ethoxy, and
sec-butyloxy groups. "Alkylene" means a straight or branched chain,
saturated, divalent aliphatic hydrocarbon group (e.g., methylene
(--CH.sub.2--) or, propylene (--(CH.sub.2).sub.3--)).
"Cycloalkylene" means a divalent cyclic alkylene group,
--C.sub.nH.sub.2n-x, wherein x is the number of hydrogens replaced
by cyclization(s). "Cycloalkenyl" means a monovalent group having
one or more rings and one or more carbon-carbon double bonds in the
ring, wherein all ring members are carbon (e.g., cyclopentyl and
cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing
the specified number of carbon atoms, such as phenyl, tropone,
indanyl, or naphthyl. "Arylene" means a divalent aryl group.
"Alkylarylene" means an arylene group substituted with an alkyl
group. "Arylalkylene" means an alkylene group substituted with an
aryl group (e.g., benzyl). The prefix "halo" means a group or
compound including one more of a fluoro, chloro, bromo, or iodo
substituent. A combination of different halo groups (e.g., bromo
and fluoro), or only chloro groups can be present. The prefix
"hetero" means that the compound or group includes at least one
ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)),
wherein the heteroatom(s) is each independently N, O, S, Si, or P.
"Substituted" means that the compound or group is substituted with
at least one (e.g., 1, 2, 3, or 4) substituents that can each
independently be a C.sub.1-9 alkoxy, a C.sub.1-9 haloalkoxy, a
nitro (--NO.sub.2), a cyano (--CN), a C.sub.1-6 alkyl sulfonyl
(--S(.dbd.O).sub.2-alkyl), a C.sub.6-12 aryl sulfonyl
(--S(.dbd.O).sub.2-aryl), a thiol (--SH), a thiocyano (--SCN), a
tosyl (CH.sub.3C.sub.6H.sub.4SO.sub.2--), a C.sub.3-12 cycloalkyl,
a C.sub.2-12 alkenyl, a C.sub.5-12 cycloalkenyl, a C.sub.6-12 aryl,
a C.sub.7-13 arylalkylene, a C.sub.4-12 heterocycloalkyl, and a
C.sub.3-12 heteroaryl instead of hydrogen, provided that the
substituted atom's normal valence is not exceeded. The number of
carbon atoms indicated in a group is exclusive of any substituents.
For example --CH.sub.2CH.sub.2CN is a C.sub.2 alkyl group
substituted with a nitrile.
[0093] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or may be presently unforeseen may
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they may be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *